Vat dyestuff of the pyrazolanthrone series



Patented Feb. 23, 1932 HEINRICH NERESHEIMEB AND SCHNEIDER, O LUDWIGSHAIEN-ON-THE- BHINE, GEBKANYQASSIGNOBS T GENERAL n. Y., A conrona'rron or nELAwA-RE Y .V A'I. DYESTUFF OF THE PYRAZOLANTHRCNE SERIES ANI INE worms, Inc, on NEW YORK,

. 1% Drawing. Application filed October 29, 1929, Serial No. 403,352, and in Germany November 13, 1828. r

The present invention relates to a process of producing new vat dyestufis containing nitrogen. a

We have found that valuable new dyestuffs 5 containing nitrogen are obtained by subjecting 2N pyrazolanthronyl benzanthrones which have a negativesubstituent in the B21- position to alkaline condensation. The 2N- p razolanthronyLbenzanthrones are obtaina le, for example, by the condensation of pyrazolanthrone or its derivatives with 2- halogenbenzanthrones which contain another negative substituent in the Bzl-position. The products obtained probably correspond to the general formula: a i

which may further be substituted. They dissolve in concentrated sulphuric acid to give from blue to bluish green solutions and dye cotton from blue to violet vats reddish violet to violet shades. For example, the dyestuif obtained by treatment of the condensation product of pyrazolanthrone and 2-chlor- Bzl-nitrobenzanthrone with alcoholic caustic potash solution dyes cotton clear reddish violet shades from a blue vat. Dyestuffs of other shades may be obtained by halogenating the products. The halogenation is'preferably effected in organic solvents and in the presence of halogcnating catalysts.

The following examples will furtherillustrate how the said invention maybe carried a out in practice, but the invention is not restricted to these examples.

The, parts are by weight.

Ewmp 1 20 parts of 2.N-pyrazolanthr0nyl-Bzl nitrobenzanthrone, obtainable'by the condensation of 2 chlor-Bzl-nitrobenzanthrone with pyrazolanthrone, which crystallizes in pale brown leaflets from nitrobenzene and probably corresponds to the formula: I

are introduced into a hot mixture of 200 parts of caustic potash and 200 parts of ethyl alcohol at 110 C. The whole is then stirred at this temperature until the formation of the dyestuff is com lete. It probably corresponds to the formu a:

ton is dyed clear reddish violet shades from a blue vat.

E wample 2 20 parts of 2.N-pyrazolanthronyl-G.Bzldichlorbenzanthrone obtainable by the condensation of pyrazolanthrone with 2.6.Bzltrichlorbenzanthrone,' obtainable by chlorinating 6.Bzl-dinitro 2 chlorbenzanthrone, which crystallizes in flat yellow leaflets from nitrobenzene and probably corresponds to the formula: y

are treated with an ethyl alcoholic solution of caustic potash as described in Example 1,

and the temperature is preferably raised to 140 C.- The dyestufi which probably corresponds to the formula:

is worked up and puriiied as described in- Example 1. It dissolves in concentrated sulphuric acid giving a bluish green coloration; Cotton is dyed violet shadesfrom a violet vat. a c r Ewampl'e 7 2O parts of 2.N-4'-benzoylaminopyrazol anthronyl Bzl nitrobenzanthrone corresponding to the-formula: O

are introduced atirom 120 to 125 a mixture of 200 parts of caustic potash and 200 parts of ethyl alcohol. The initial material is obtained for example by the condensation of .Z-chlor-Bzl-nitrobenzanthrone with 4-benzoylaminopyrazolanthrone, obtainable by treating l-chlori-benzoylaminoanthraquinone with hydrazin hydrate, crystallizing in yellow brown leaflets from trichlorbenzene and crystallizes from nitrobenzene in the form of yellow brown needles 7.. .1

henthe reaction is complete, the dyestufl is worked up as described in Example 1 and I purified; for example, by crystallization from nitrobenzene. It probably corresponds to the'formula:

dissolves inconcentrated sulphuric acid giv ing a blue coloration and-dyes cotton violet shades from a violet vat. Y

xample 4 25 parts of the product obtainable according to Example Larei treated with 37 parts of sulphur l' chloride in 250 parts of nitrobenzene, a ter the addition of Lparts of pyridine, for 2 hours at about 50 C. and then 7 for 1 hour at 60 C. The warm reaction mixture is filtered and the reaction product washed with nitrobenzene and benzene. The dyestuff made into a paste by usual methods dissolves in concentrated sulphurioacidqto give a greenish bluesolution and dyes cotton from a blue vatired violetshades. What we claimis:'- V W1 4 I 1 The process of producing nitrogenous vat-dyestuffs; which comprises treating a. 2 .N- pyrazol anthronylbenzanthrone containing a halogenioranitro group in the Bjzl -position with an alkaline condensing agent. i

2. The process ofproducing nitrogenous vat dyestufl's, which comprises treating a. ZN-pyrazolanthronylbenzanthrone containing a halogen or a nitro group in theBzl-posiition with an alcoholic. caustic alkali melt. 3; p The process of producing afnitrogenou's vat dyestufi', which. comprises treating 2N- yrazolanthronyl" Bzl' nitrobenzanthrone with an alcoholic caustic "potash melt."

4. The process of producing nitrogenous vat dyestuffs which comprises treatin a 2N- pyrazolanthronylbenzanthrone, contalnin a halongen or a nitro group in the Bzl-positlon with an alkaline condenslng agent and treating the condensation product with a halogenating agent.

5. As new articles of manufacture vat dyestufi's probably corresponding to the general formula:

vat dyestufl probably corresponding to the formula:

@ dissolving in concentrated sulfuric acid givll ing a blue coloration and dyeing cotton violet shades from a violet vat.

In testimony whereof we have hereunto set our hands.

HEINRICH NERESHEIMER. WILHELM SCHNEIDER.

which may contain substituents of the group consisting of halogen and acylamino, the said dyestuffs dissolvin in concentrated sulphuric acid to give from lue to bluish green solutions and dyeing cotton from reddish violet to violet shades from blue to violet vats.

. 6. As a new article of manufacture the vat dyestufl probably corresponding to the formula:

dissolving in concentrated sulphuric acid to give a blue solution and dyeing cotton from a blue vat reddish violet shades.

7. As a new article of manufacture, the vat dyestufi' probably corresponding to the formula:

dissolving in concentrated sulfuric acid giving a bluish green coloration and dyeing cotton violet shades from a violet vat.

8. As a new article of manufacture, the 

